EP0121376A2 - Process for upgrading a heavy viscous hydrocarbon - Google Patents
Process for upgrading a heavy viscous hydrocarbon Download PDFInfo
- Publication number
- EP0121376A2 EP0121376A2 EP84301888A EP84301888A EP0121376A2 EP 0121376 A2 EP0121376 A2 EP 0121376A2 EP 84301888 A EP84301888 A EP 84301888A EP 84301888 A EP84301888 A EP 84301888A EP 0121376 A2 EP0121376 A2 EP 0121376A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- solvent extraction
- visbreaker
- line
- fraction
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 91
- 230000008569 process Effects 0.000 title claims abstract description 88
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 43
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 42
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 71
- 229920005989 resin Polymers 0.000 claims abstract description 71
- 239000000047 product Substances 0.000 claims abstract description 63
- 238000000638 solvent extraction Methods 0.000 claims abstract description 51
- 238000004821 distillation Methods 0.000 claims abstract description 47
- 239000003921 oil Substances 0.000 claims description 58
- 239000002904 solvent Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 17
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- 239000012263 liquid product Substances 0.000 abstract description 3
- 238000009877 rendering Methods 0.000 abstract 1
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- 239000001257 hydrogen Substances 0.000 description 30
- 229910052739 hydrogen Inorganic materials 0.000 description 30
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- 229910052751 metal Inorganic materials 0.000 description 23
- 239000002184 metal Substances 0.000 description 23
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- 238000009835 boiling Methods 0.000 description 18
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 238000004939 coking Methods 0.000 description 12
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- 238000004227 thermal cracking Methods 0.000 description 6
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- 238000013461 design Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
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- 150000002431 hydrogen Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000004058 oil shale Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000003415 peat Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000011345 viscous material Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 238000006477 desulfuration reaction Methods 0.000 description 1
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- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one thermal cracking step
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
- C10G67/049—The hydrotreatment being a hydrocracking
Definitions
- the present invention relates to processes for upgrading heavy viscous hydrocarbons, such as viscous crude oils, bitumens from tar sands, hydrocarbons derived from coal, lignite, peat or oil shale, residuum resulting from the atmospheric and/or vacuum distillation of lighter crude oils, heavy residues from solvent extraction processes, and the like.
- Such processes include, for example, the treating to reduce the viscosity of heavy viscous crudes which are impractical to pump at ambient temperatures to obtain a product which is practical to pump through conventional pipe lines.
- some of the upgrading processes include reducing the metals, particularly nickel and vanadium, and Conradson carbon content while reducing the specific gravity.
- a large number of processes are available for treating heavy, viscous hydrocarbons, such as Boscan crude from Venezuela or Cold Lake crude from Canada, to obtain an upgraded, product with lower viscosity, specific gravity, metals content, and Conradson carbon content.
- these processes may be grouped into two broad classes: (1) the solvent extraction processes which remove high carbon viscous materials and (2) the conversion processes.
- the solvent extraction processes rely on physical separation, not chemical conversion.
- the metals, sulfur, and Conradson carbon contents are highest in the asphaltene fraction, next highest in the resin fraction, and smallest in the oil fraction.
- the relative amounts of the asphaltene, resin and oil fractions and the corresponding properties thereof can be varied over a wide range by changing solvents and operating conditions in the solvent extraction unit.
- the metal and Conradson carbon content of the resin fraction is usual- ' 1y increased to the point where the resin fraction is not a desirable material for subsequent catalytic processing such as catalytic cracking or hydrocracking.
- the two-stage unit may be operated to include the resins in varying degrees with the asphaltenes or with the oils.
- the metals and Conradson carbon contents of the fractions would vary accordingly. It is also possible to operate four or more stages of a solvent extraction unit. Varying cuts can be made depending on operation with the heaviest cuts containing the highest molecular weight materials, the greatest viscosity, and the highest metals and Conradson carbon content.
- the second broad class includes processes which convert the high boiling viscous hydrocarbons to lighter products. These conversion processes can be grouped into three categories: (1) processes which employ a high hydrogen partial pressure; (2) thermal cracking processes which prevent coke formation by special design and by limiting conversion; and (3) processes which produce coke.
- the thermal cracking processes are generally less expensive than those in the other categories but generally produce a lower yield of residual and gas-free products.
- "Residual and gas-free products” are defined herein as total products, less (1) C 2 and lighter gas, (2) ⁇ oke, (3) liquid boiling above 1050°F containing more than 10% Conradson carbon, and (4) Conradson carbon content of other products.
- the yields of thermal cracking processes are limited by feedstock quality, product quality, and coke formation. For a given feedstock, the greatest conversion may be obtained by increasing the severity to the level where the product quality or rate of coke formation become unacceptable. The rate of coke formation is increased as the resins and high moleculer weight oils, which act to peptize and maintain the asphaltenes dispersed, are cracked.
- Hydroconversion processes generally produce the highest yield of residual and gas-free products, but are also much more costly both from an investment and an operating cost standpoint than thermal cracking processes.
- the hydroconversion processes require a high investment because a hydrogen production facility is required to supply hydrogen and high hydrogen partial pressure is required in the hydroconversion unit to either suppress coke formation on the catalyst or to accomplish the hydrogen addition noncatalytically.
- Utilities costs for typical hydroconversion processes are high because of the high cost of hydrogen compression and the multiplicity of steps involved. Additionally, operating costs are increased where high metals content of heavy crudes such as Boscan and Cold Lake result in catalyst deactivation.
- the crude is usually subjected to successive atmospheric and vacuum distillation to reduce the amount charged to the very expensive high pressure residual hydroconversion step.
- This hydroconversion requires that the bottoms from the vacuum :distillation be further heated to hydroprocessing reactor temperature. Part of the effluent from the hydroconversion reactor is then cooled to produce a hydrogen recycle stream with low hydrocarbon content. The remaining effluent is then further heated for distillation and followed, in some cases, by solvent extraction to produce a heavy residual together with gas oil and lighter products.
- Processes such as delayed and fluid coking can be heat integrated to avoid repeated successive heating and cooling steps.
- yield of residual and gas-free products of such coking processes are generally less than hydroconversion processes.
- olefinic content as indicated by the bromine number of coking products is usually relatively high resulting in a high hydrogen consumption in subsequent refining processes to produce finished products.
- the present invention teaches a process for upgrading a heavy viscous hydrocarbon including visbreaking, distillation, and solvent extraction steps wherein at least a portion of a heavy viscous hydrocarbon is visbroken and fed to a distillation step for fractionation, a heavier fraction for the distillation step is fed to a solvent extraction step and a fraction from the solvent extraction step which contains resins is combined with the feed to the visbreaker to permit higher conversion in the visbreaker.
- This process offers a significant yield and quality improvement over processes of similar cost and complexity; furthermore, much lower investment and operating costs are required than for processes which produce similar yields and product quality.
- One advantage of the invention is that increased visbreaking conversion is possible due to the increased resin content of the visbreaker feed resulting from this process.
- the .resins crack at a rate approximately ten times greater than the average of the high molecular weight-oils.
- a second advantage of the process of this invention compared to the conventional solvent extraction scheme is improved product quality.
- a residual and gas-free product can be produced with lower metals and Conradson carbon content and lower viscosity than by the conventional solvent extraction process.
- a synthetic crude suitable for pumping through conventional pipelines may be produced in much higher yield than by the conventional solvent extraction process.
- a third advantage of the process of this invention is hydrogen conservation. Compared to other thermal cracking and coking processes, the liquid product from the process of this invention has a higher hydrogen content than that of competing processes; thus the downstream :hydrotreating costs are significantly less.
- Another advantage is the low capital and operating cost which results from utilizing this unique combination of conventional and highly proven process steps with minimal complexity and a high degree of energy efficiency.
- a heavy viscous hydrocarbon input or feedstock in line 10 is fed through a visbreaker heater 18 into a distillation column 14. Bottoms from the distillation column are withdrawn in line 20 and supplied to a solvent extraction unit 26.
- the distillation column may be replaced by any other fractionation apparatus, for example those of a centrifugal type fractionating apparatus.
- the solvent extraction unit 26 is a conventional plant; for example, such as that illustrated in U.S. Patent No. 4,239,616, which in a first separation procedure separates asphaltenes from the feed, and in a second separation stage separates resins from the remainder leaving an oil product from which the solvent is separated.
- the solvent or solvents used and the percent of oil and resin removed from the heavy viscous material are dependent upon the economic yield-product quality relationship for the particular application.
- Solvents employed may include paraffin hydrocarbons containing from 3 through 9 carbon atoms, such as 'propane, butane, pentane, hexane, heptane, octane and nonane; and/or mono-olefin hydrocarbons containing from 3 to 9 carbon atoms such as propene, butene, pentene, hexene, heptene, octene and nonene and/or aromatic hydrocarbons having normal boiling points below 310°F (154°C) such as benzene, toluene, ortho-, meta- and para-xylene, and isopropyl benzene.
- paraffin hydrocarbons containing from 3 through 9 carbon atoms such as 'propane, butane, pentane, hexane, heptane, octane and nonane
- mono-olefin hydrocarbons containing from 3 to 9 carbon atoms such
- the lower boiling paraffin hydrocarbons such as propane
- the lower boiling paraffin hydrocarbons result, in the production of a superior quality oil but of lower quantity.
- Increasing the boiling range or decreasing the hydrogen content of the solvent results in a decreased yield of asphaltenes and a higher yield of oil of poorer quality.
- the solvent extraction unit 26 produces two or more streams depending on the number of stages in the unit. At least a portion of one of the lighter streams which contains resins, the second (resin) stream in a typical three-stage unit, is combined with the material forming the :feed for the visbreaker heater 18 where at least a portion of the material is thermally cracked into lighter components.
- the visbreaker heater effluent is then fed to a distillation column 14 for fractionating. Gas and lighter liquid hydrocarbons are withdrawn in line 30 as overhead from the distillation column 14 and separated by the gas/liquid separator 32 into a gas stream in line 34 and a lighter liquid hydrocarbon stream in line 40. Intermediate liquid hydrocarbons are withdrawn in a side stream in line 48 from the distillation column 14.
- the three-stage solvent extraction unit 26 shown in Figure 1 in addition to the resin stream in line 28, produces a solvent-extracted oil stream in line 56 and an asphaltene product stream in line 58. A portion of the resin may be withdrawn as a product stream in line 60.
- the product streams 40, 48, and 56 may be used individually, or may be combined as shown in Figure 1 to form a single synthetic crude product stream in line 62.
- the present invention can be utilized for upgrading a variety of heavy viscous hydrocarbons including viscous crude oils, bitumens from tar sands, hydrocarbons derived from coal, lignite, peat or oil shale, re- sidium resulting from the vacuum or atmospheric distillation of lighter crude oils, heavy residues from solvent extraction processes, and the like.
- the basic process illustrated in Figure 1 is particularly suitable for use where the heavy viscous hydrocarbon feed has been previously processed leaving only those components boiling above 650°F (343°C) or higher in the feed.
- a modified process which would be more suitable for smaller units which process crude oils which have a significant amount of lighter fractions in the oil is shown in Figure 2.
- a heavy viscous hydrocarbon input or feedstock in line 10 is fed through conventional preheat exchangers 70, 72, 74, 78, and/or 80 and/or a feedstock heater 12 into a feedstock flash zone in a lower portion of a distillation column 14.
- Feedstock flash bottoms withdrawn in line 16 are passed through a visbreaker heater 18 and then into a visbreaker flash zone or intermediate zone of the distillation column 14. Bottoms from the 'v isbreaker flash zone are withdrawn in line 20 and supplied to solvent extraction unit 26.
- the solvent extraction unit 26 produces a stream which contains a resin product at least a portion of which is combined with the material forming the feed for the visbreaker furnace 18; for example, the resin in line 28 is fed into the bottom of the distillation column 14 for combining with the feedstock bottoms which are subsequently withdrawn in line 16 to feed the visbreaker heater 18.
- Gas and naphtha are withdrawn in line 30 as overhead from the distillation column 14 and separated by the separator 32 into a gas stream in line 34 and a naphtha stream in line 36.
- a portion of the naphtha stream in line 36 is fed back to the top of the column 14 by line 38 as a reflux stream while the remaining portion forms a naphtha product in line 40.
- Gas oil is withdrawn in a side stream in line 42 from the distillation column 14, with portions in lines 44 and 46 being supplied back to the distillation column as reflux streams. Part of stream 46 may be used as a quench 47 for the transfer line 19 from the visbreaker heater. The remaining portion of the light gas oil forms a product stream in line 48.
- the solvent extraction unit 26 in addition to ' the resin stream in line 28, produces a solvent-extracted oil stream in line 56 and an asphaltene product stream in line 58. A portion of the resin may be withdrawn as a product stream in line 60.
- the product streams 40, 48, and 56 may be used individually, or may be combined as shown in Figure 2 to form a single synthetic crude product stream in line 62.
- the visbreaker heater may be of conventional coil only or coil plus soaking drum design or of any other available type.
- the term visbreaker heater as used herein includes all equipment associated with the visbreaker including the soaking drum where utilized but excluding the fractionator.
- the visbreaker heater heats the feedstock flash zone bottoms which includes the recycled resins to a temperature in the range from about 850 to 920°F (454 to 493°C). Generally a temperature near the lower end of the range will be utilized in the soaking :drum type visbreaker whereas a temperature near the higher end of the range will be employed in coil type visbreaking.
- the conversion within the visbreaker heater 18 is limited to avoid coke formation.
- Adding hydrogen to the visbreaking process improves yields. It also may be added to act as a chain reaction quench, to control feedstock residence time in the coil, to increase the amount flashed at the entrance of the distillation column, and to achieve some desulfurization.
- the preferred hydrogen addition point is usually near the furnace coil outlet where its chain-quenching effect is important in reducing coke formation.
- the hydrogen, if added may be introduced at any point in the visbreaking process, depending on operating conditions and operator preference.
- the visbreaker effluent flashes up to a cut point as high as 840°F (449°C), depending on the temperature and hydrocarbon partial pressure in the visbreaker flash zone.
- the cut point and temperature in the visbreaker flash zone are selected as high as the coking tendency of the hydrocarbon will permit.
- a vacuum tower and vacuum heater may be added.
- the crude heater and crude flash zone in the distillation column 14 may be eliminated and the flow scheme as shown in Figure 3 may be utilized.
- the heavy viscous hydrocarbon feedstock in line 10 is fed through preheat exchangers to an optional hydrogen contactor vessel/and then through a visbreaker heater 18 to the flash zone in the distillation column 14. Bottoms from the flash zone are withdrawn in line 20 and :are at least partially vaporized in a vacuum heater 21 and are then fed through line 23 into a vacuum column 22. Use of the vacuum heater will increase the cut point of the heavy gas oil and decrease the amount of the bottoms from the vacuum column through line 24. This will decrease the required size of the solvent extraction unit 26.
- the solvent extraction unit 26 produces a stream which contains resin product at least a portion of which is combined with the material forming the feed for the visbreaker heater 18.
- Gas and naphtha are withdrawn in line 30 as overhead from the distillation column 14 and separated by the separator 32 into a gas stream in line 34 and a naphtha stream in line 36.
- a portion of the naphtha stream in line 36 is fed back to the top of the distillation column 14 by line 38 as a reflux stream while the remaining portion forms a naphtha product in line 40.
- Light gas oil is withdrawn in a side stream in line 42 from the distillation column 14 with portions in lines 44 and 46 being supplied back to the distillation column as reflux streams. Part of stream 46 may be used as a quench 47 for the transfer line 19 from the visbreaker heater. The remaining portion of the light gas oil forms a product stream in line 48.
- the liquid side stream from the vacuum column 22 is withdrawn as a heavy gas oil stream in line 50, a portion of which is recycled back as a reflux stream 52 with the remainder forming a product stream in line 54.
- the solvent extraction unit 26 in addition to the resin stream in line 28, produces a solvent-extracted oil stream in line 56 and an asphaltene product stream in line 58.
- a portion of the resin may be withdrawn as a prod- u ct stream in line 60.
- the product streams 40, 48, 54 and 56 may be used individually, or may be combined to form one synthetic crude or several upgraded product streams.
- Conventional heat exchangers 70, 72 , 74, 76 and/or 78 may be provided to recover process heat from the distillation column overhead, light gas oil product, light gas oil pumparound, vacuum column pumparound, and the solvent-extracted oil stream, respectively.
- hydrogen may be added to the vis- :breaker feed streams 10, 16, or as shown in Fig. 3, 17.
- a contactor vessel 13 may optionally be utilized for this or the hydrogen may be added directly in the pipeline.
- a typical flow scheme for upgrading heavy viscous crudes such as Cold Lake, Athabasca, Lloydminister, Tia Juana, Pesado or Lagotreco, is shown in Figure 4.
- the hydrocarbon feedstock is heated to a temperature in the range from about 650 to 700°F (343 to 371°C).
- Conventional heat exchangers 70, 72, 74, 76, 78 and/or 80 may be provided to recover process heat from distillation column overhead, light gas oil product, light gas oil pumparound, vacuum column pumparound, solvent-extracted oil stream, and vacuum bottoms recyle, respectively. Additional heating then occurs within the crude heater 12 to bring the feedstock to the desired flash temperature for the distillation column 14.
- Crude flash bottoms withdrawn in line 16 are passed through the visbreaker heater 18 and then into a visbreaker flash zone or intermediate zone of the distillation column 14. Bottoms from the visbreaker flash zone are withdrawn in line 20 and flashed as deeply as economically feasible within the adiabatic vacuum column 22.
- a 950°F (510°C) cut point can usually be obtained at a 40mm hydrocarbon partial pressure where the feed from the bottoms of the visbreaker flash zone contains only material with a boiling point above 650°F (343°C) and with its temperature at about 750°F (399°C).
- the cut point in the visbreaker flash ,zone of the distillation column 14 is selected to be as high as practical to minimize the size of the vacuum column 22.
- the three-stage solvent extraction unit 26 produces a resin product at least a portion of which is combined with the material forming the feed for the visbreaker heater 18; for example, the resin in line 28 is fed into the bottom of the column 14 for combining with the -crude bottoms which are subsequently withdrawn in line 16 to feed the visbreaker heater 18.
- Gas and naphtha are withdrawn in line 30 as overhead from the distillation column 14 and separated by the separator 32 into a gas stream in line 34 and a naphtha stream in line 36.
- a portion of the naphtha stream in line 36 is fed back to the top of the column 14 by line 38 as a reflux stream while the remaining portion forms a naphtha product in line 40.
- Light gas oil is withdrawn in a side stream in line 42 from the distillation column 14 with portions in lines 44 and 46 being supplied back to the distillation column 14 as reflux streams.
- Part of stream 46 may be used as a quench 47 for the transfer line 19 from the visbreaker heater 18.
- vacuum bottoms may be recycled to the visbreaker flash zone through line 49 or heavy gas oil may be used as a quench. The choice of quench schemes will depend on the feedstock characteristics and operator preference.
- the remaining portion of the light gas oil forms a product stream in line 48.
- the .liquid sidestream from the vacuum column 22 is withdrawn as a heavy gas oil stream in line 50, a portion of whirh is recycled back as a reflux stream 52 with the remainder forming a product stream in line 54.
- the three-stage solvent extraction unit 26 shown in Figure 4 in addition to the resin stream in line 28, produces a solvent-extracted oil stream in line 56 and an asphaltene product stream in line ' 58. A portion of the resin may be withdrawn as a product stream in line 60.
- the product streams 40, 48, 54 and 56 may be used individually, or may be combined to form a single synthetic crude product stream.
- the improved process of the present invention renders possible the obtaining of residual and gas-free product yields greater than other n onhydroprocessing schemes and comparable to processes employing. high pressure hydroconversion.
- the prior art hydroconversion processes are much more costly both from an investment and operating standpoint, particularly due to catalyst cost, when compared with the present invention.
- Synthetic crude yield of prior art delayed coking processes are typically 5 to 7% by weight less on feed than the present inven- :tion, and the synthetic crude yield of prior art fluid coking processes are typically 2 to 4% by weight less.
- the increase in resin content of the feed to the visbreaker heater 18 is principally responsible for the substantially increased yields of the present invention.
- the resins are found to act as peptizing agents and keep the very high molecular weight asphaltenes suspended. This maintenance in suspension of asphaltenes reduces the coking tendency in the visbreaker heater enabling a substantial increase in the conversion within the visbreaker heater without coking. Thus, a substantially higher conversion can be obtained in the visbreaker than without resin recycle. A high yield of synthetic crude of good quality is thus obtained utilizing relatively inexpensive thermal conversion rather than the more expensive hydroconversion processes.
- Another advantage of the present invention is that the synthetic crude or products are relatively low in metal content and thus can be handled by conventional downstream processing such as catalytic cracking or hydrocracking.
- Metals content of some heavy crudes, such as Boscan and Cold Lake, are very high. High metals content results in catalyst deactivation due to pore plugging and screening of catalytically active sites if these high metal feeds are charged to a catalytic process.
- prior art processes utilizing catalytic hydroconversion for primary conversion incur large catalyst costs due to the high metals content.
- Still another advantage of the invention is the avoidance of cooling and reheating during process flow.
- the feeds to the distillation column 14 are progressively heated, and, except where a vacuum heater is employed, the flows from the distillation column generally are progressively cooled resulting in substantially lower utility costs.
- some heating may also be required within the solvent extraction unit.
- Prior art hydroconversion processes generally require reheating and cooling producing substantially increased utility costs.
- Prior art delayed and fluid coking processes can be integrated to produce progressive heating and cooling similar to the present invention; however, the synthetic crude yield of such processes is substantially less than the present invention.
- the recycle resins typically have a hydrogen content 15 to 20% higher than asphaltenes; the hydrogen content of a typical resin is 9.8 to 10.2% by weight, while asphaltenes have a hydrogen content of only 8.2 to 8.7% by weight.
- the bromine number, which measures the olefinic content, of a product from a fluid coking process is typically more than twice as high as that of a product produced in the present process, resulting in a much higher hydrogen consumption during subsequent hydroprocessing.
- a significant advantage of the process of this invention is that light hydrocarbon yields (C l -C 3 ) are approximately half of those listed in the literature for severe cyclic visbreaking to achieve a comparable tar yield, and only one fourth that of fluid coking. Since light hydrocarbons contain a high percentage of hydrogen, it is apparent that the liquid product from the process of this invention has a higher hydrogen content than that of competing processes; thus, downstream hydrotreating costs are significantly less. Thus conservation of hydrogen and rejection of only the minimum hydrogen content asphaltene results in minimum downstream refining costs.
- Run -1 represents a visbreaker run with no resin recycle at typical conditions for a commercial visbreaker.
- Run 2 is a visbreaker run with resin recycle equal to 20% of the total visbreaker feed at about the same severity as Run 1.
- Run 3 is a visbreaker run at higher severity than Runs 1 and 2 and with resin recycle equal to 20% of the total visbreaker feed; theory being that resins stabilize the asphaltenes in the oil and reduce coke formation in the visbreaker furnace.
- Solvent extraction data for 950°F + fraction from the various visbreaker runs are presented in Table II.
- Asphaltenes were determined by mixing a finely ground sample of the 950°F+ fraction with 20 volumes of n-pentane per volume of sample at room temperature for six hours; :the undissolved material was filtered using fine filter paper and washed with fresh n-pentane until the filtrate was clear. After evaporating the n-pentane on the surface of the undissolved material in a stream of nitrogen at low temperature, the material was weighed and reported as the asphaltene yield of the 950°F+ fraction. The n-pentane in the filtrate from the previously described determination of asphaltenes was evaporated to bring the solvent/feed ratio back to 20/1.
- the resultant material was charged to a closed vessel equipped with a valve which was then attached to an apparatus which provided agitation by mechanical rocking and which was fitted with a heating mantle with close temperature control. The temperature was raised to 375°F and a resin phase was withdrawn. The resin and oil yields were determined by evaporating the n-pentane solvent from the respective fractions. From analysis of the resin fraction, it should be noted that the resin is very high in metals (157-240 ppm wt) and would not be a good hydrocracker or hydrotreater feed.
- yield data for the recycled resin can be derived. This calculation is shown'in Table III. It should be noted that at approximately the same severity as Run 1, for Run 2 the resin went approximately half to-asphalt and half to solvent extracted oil. The apparent negative yield from recycle resin of the 650-950°F fraction in Run 2 is probably accounted for by experimental error.
- Table IV presents a summary of the results of Runs 1, 2, and 3 with respect to the disposition of the 650°F + fractions.
- a further extension of this concept would be to produce a combined resin and oil fraction from the 950°F+, or 1050°F+ by revising vacuum column operating conditions, material and recycle that fraction to extinction; in this case there would be zero yield of the 950°F+, or 1050°F+, oil and all products, other than the asphaltene fraction, would be distillate products very low in Conradson carbon and metals content.
- the recycle bottoms in line 16 have a boiling point greater than 650°F (343°C).
- the bottoms from the visbreaker flash zone in line 20 have a boiling pont above 700°F (371°C).
- the naphtha in line 36 has a boiling point less than 400°F (204°C) while the boiling range for the light gas oil in line 48 is in the range from 400 to 700°F (204 to 371°C).
- the heavy gas oil in line 54 has a boiling point in the range from 700 to 950°F (371 to 510°C).
- the synthetic crude product in line 62 forms a stream of about 17,360 barrels per day or approximately 86.8% volume of the feedstock at 21.8° API and 20 centistokes viscosity at 100°F.
- the gas in line 34 forms about 1.3% by weight
- the naptha in line 40 forms about 13.2% by volume
- the light gas oil in line 48 is about 30.8% by volume
- the heavy gas oil in line 54 is about 22.3% by volume
- the solvent-extracted oil in line 56 is about 20.5% by volume
- the asphaltene in line 58 is about 14.9% by volume of the total input.
- About 4.9% of the total volume is recycled in line 28 as resin.
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Abstract
Description
- The present invention relates to processes for upgrading heavy viscous hydrocarbons, such as viscous crude oils, bitumens from tar sands, hydrocarbons derived from coal, lignite, peat or oil shale, residuum resulting from the atmospheric and/or vacuum distillation of lighter crude oils, heavy residues from solvent extraction processes, and the like. Such processes include, for example, the treating to reduce the viscosity of heavy viscous crudes which are impractical to pump at ambient temperatures to obtain a product which is practical to pump through conventional pipe lines. Additionally, some of the upgrading processes include reducing the metals, particularly nickel and vanadium, and Conradson carbon content while reducing the specific gravity.
- A large number of processes are available for treating heavy, viscous hydrocarbons, such as Boscan crude from Venezuela or Cold Lake crude from Canada, to obtain an upgraded, product with lower viscosity, specific gravity, metals content, and Conradson carbon content. Generally these processes may be grouped into two broad classes: (1) the solvent extraction processes which remove high carbon viscous materials and (2) the conversion processes.
- The solvent extraction processes rely on physical separation, not chemical conversion. In a typical three-stage solvent extraction process where oils, resins, and asphaltenes are produced as separate fractions, the metals, sulfur, and Conradson carbon contents are highest in the asphaltene fraction, next highest in the resin fraction, and smallest in the oil fraction. The relative amounts of the asphaltene, resin and oil fractions and the corresponding properties thereof, can be varied over a wide range by changing solvents and operating conditions in the solvent extraction unit. When producing a minimum amount of the asphaltene fraction, it generally happens that the metal and Conradson carbon content of the resin fraction is usual- '1y increased to the point where the resin fraction is not a desirable material for subsequent catalytic processing such as catalytic cracking or hydrocracking.
- In order to produce a solvent extracted oil with acceptable metal and Conradson carbon levels for catalytic processing, it is necessary to limit the yield of the oil fraction and increase the yields of the resin and asphaltene fractions. Since the latter two fractions generally must be used as a residual fuel of very low value, a serious economic penalty on the utilization of solvent extraction processes results.
- Similar results are obtained with a two-stage solvent extraction unit. The two-stage unit may be operated to include the resins in varying degrees with the asphaltenes or with the oils. The metals and Conradson carbon contents of the fractions would vary accordingly. It is also possible to operate four or more stages of a solvent extraction unit. Varying cuts can be made depending on operation with the heaviest cuts containing the highest molecular weight materials, the greatest viscosity, and the highest metals and Conradson carbon content.
- The second broad class includes processes which convert the high boiling viscous hydrocarbons to lighter products. These conversion processes can be grouped into three categories: (1) processes which employ a high hydrogen partial pressure; (2) thermal cracking processes which prevent coke formation by special design and by limiting conversion; and (3) processes which produce coke.
- The thermal cracking processes are generally less expensive than those in the other categories but generally produce a lower yield of residual and gas-free products. "Residual and gas-free products" are defined herein as total products, less (1) C2 and lighter gas, (2) εoke, (3) liquid boiling above 1050°F containing more than 10% Conradson carbon, and (4) Conradson carbon content of other products. The yields of thermal cracking processes are limited by feedstock quality, product quality, and coke formation. For a given feedstock, the greatest conversion may be obtained by increasing the severity to the level where the product quality or rate of coke formation become unacceptable. The rate of coke formation is increased as the resins and high moleculer weight oils, which act to peptize and maintain the asphaltenes dispersed, are cracked. This causes the asphaltenes to become incompatible with the surrounding constituents, to start to form a sediment, to increase in number and/or size due to polymerization and/or condensation reactions, and to increase the rate of coke formation. This also affects the quality of products from thermal cracking processes as the asphaltenes and sediments detract from product quality by adversly affecting product stability and compatability with blending stocks.
- Hydroconversion processes generally produce the highest yield of residual and gas-free products, but are also much more costly both from an investment and an operating cost standpoint than thermal cracking processes. The hydroconversion processes require a high investment because a hydrogen production facility is required to supply hydrogen and high hydrogen partial pressure is required in the hydroconversion unit to either suppress coke formation on the catalyst or to accomplish the hydrogen addition noncatalytically. Utilities costs for typical hydroconversion processes are high because of the high cost of hydrogen compression and the multiplicity of steps involved. Additionally, operating costs are increased where high metals content of heavy crudes such as Boscan and Cold Lake result in catalyst deactivation.
- In a typical hydroconversion process, the crude is usually subjected to successive atmospheric and vacuum distillation to reduce the amount charged to the very expensive high pressure residual hydroconversion step. This hydroconversion requires that the bottoms from the vacuum :distillation be further heated to hydroprocessing reactor temperature. Part of the effluent from the hydroconversion reactor is then cooled to produce a hydrogen recycle stream with low hydrocarbon content. The remaining effluent is then further heated for distillation and followed, in some cases, by solvent extraction to produce a heavy residual together with gas oil and lighter products. These repeated heating and cooling steps result in relatively high investment and operating costs.
- Processes such as delayed and fluid coking can be heat integrated to avoid repeated successive heating and cooling steps. However the yield of residual and gas-free products of such coking processes are generally less than hydroconversion processes. Further the olefinic content as indicated by the bromine number of coking products is usually relatively high resulting in a high hydrogen consumption in subsequent refining processes to produce finished products.
- The present invention teaches a process for upgrading a heavy viscous hydrocarbon including visbreaking, distillation, and solvent extraction steps wherein at least a portion of a heavy viscous hydrocarbon is visbroken and fed to a distillation step for fractionation, a heavier fraction for the distillation step is fed to a solvent extraction step and a fraction from the solvent extraction step which contains resins is combined with the feed to the visbreaker to permit higher conversion in the visbreaker.
- This process offers a significant yield and quality improvement over processes of similar cost and complexity; furthermore, much lower investment and operating costs are required than for processes which produce similar yields and product quality.
- One advantage of the invention is that increased visbreaking conversion is possible due to the increased resin content of the visbreaker feed resulting from this process. During visbreaking, the .resins crack at a rate approximately ten times greater than the average of the high molecular weight-oils. For this reason it is quite beneficial to have the significantly higher concentration of resins which result from resin recycle, particularly near the outlet of the visbreaking coil, to act as a peptizing agent to help maintain the asphaltenes in suspension and avoid the formation of coke. This allows the visbreaker to be operated at even greater severity allowing even greater conversion rates and thus higher yields of residual and gas free products.
- A second advantage of the process of this invention compared to the conventional solvent extraction scheme is improved product quality. A residual and gas-free product can be produced with lower metals and Conradson carbon content and lower viscosity than by the conventional solvent extraction process. Thus, a synthetic crude suitable for pumping through conventional pipelines may be produced in much higher yield than by the conventional solvent extraction process.
- A third advantage of the process of this invention is hydrogen conservation. Compared to other thermal cracking and coking processes, the liquid product from the process of this invention has a higher hydrogen content than that of competing processes; thus the downstream :hydrotreating costs are significantly less.
- Another advantage is the low capital and operating cost which results from utilizing this unique combination of conventional and highly proven process steps with minimal complexity and a high degree of energy efficiency.
- Other advantages of the invention will be apparent from the following description of the preferred embodiment taken in conjunction with the accompanying drawings.
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- Figure 1 is a flow diagram of a process for upgrading hydrocarbons in accordance with the invention. This basic flow scheme is particularly suitable for use where the heavy viscous hydrocarbon feed has been previously processed leaving only those components boiling above 650°F (343°C) or higher in the feed.
- Figure 2 is a flow diagram of a modified process for upgrading hydrocarbons in accordance with the invention. It is particularly suitable for smaller units which process crude oils which have a significant amount of lighter fractions in the oil.
- Figure 3 is a flow diagram of another modified process for upgrading hydrocarbons in accordance with the invention. It includes a vacuum column for reducing the amount of material which must be processed in -the -solvent extraction unit. However, because it does not have a crude or feedstock heater, it is particularly suitable for larger units which process heavy viscous hydrocarbons that do not have a significant percentage of compounds boiling below 650°F (343°C).
- Figure 4 is a flow diagram of another modified process for upgrading hydrocarbons in accordance with the invention. 'It is particularly suitable for larger units processing crude oils.
- As illustrated in Figure 1, a heavy viscous hydrocarbon input or feedstock in
line 10 is fed through avisbreaker heater 18 into adistillation column 14. Bottoms from the distillation column are withdrawn in line 20 and supplied to asolvent extraction unit 26. Alternatively, the distillation column may be replaced by any other fractionation apparatus, for example those of a centrifugal type fractionating apparatus. - The
solvent extraction unit 26 is a conventional plant; for example, such as that illustrated in U.S. Patent No. 4,239,616, which in a first separation procedure separates asphaltenes from the feed, and in a second separation stage separates resins from the remainder leaving an oil product from which the solvent is separated. The solvent or solvents used and the percent of oil and resin removed from the heavy viscous material are dependent upon the economic yield-product quality relationship for the particular application. Solvents employed may include paraffin hydrocarbons containing from 3 through 9 carbon atoms, such as 'propane, butane, pentane, hexane, heptane, octane and nonane; and/or mono-olefin hydrocarbons containing from 3 to 9 carbon atoms such as propene, butene, pentene, hexene, heptene, octene and nonene and/or aromatic hydrocarbons having normal boiling points below 310°F (154°C) such as benzene, toluene, ortho-, meta- and para-xylene, and isopropyl benzene. In general, the lower boiling paraffin hydrocarbons, such as propane, result, in the production of a superior quality oil but of lower quantity. Increasing the boiling range or decreasing the hydrogen content of the solvent results in a decreased yield of asphaltenes and a higher yield of oil of poorer quality. - The
solvent extraction unit 26 produces two or more streams depending on the number of stages in the unit. At least a portion of one of the lighter streams which contains resins, the second (resin) stream in a typical three-stage unit, is combined with the material forming the :feed for thevisbreaker heater 18 where at least a portion of the material is thermally cracked into lighter components. The visbreaker heater effluent is then fed to adistillation column 14 for fractionating. Gas and lighter liquid hydrocarbons are withdrawn inline 30 as overhead from thedistillation column 14 and separated by the gas/liquid separator 32 into a gas stream inline 34 and a lighter liquid hydrocarbon stream inline 40. Intermediate liquid hydrocarbons are withdrawn in a side stream inline 48 from thedistillation column 14. The three-stagesolvent extraction unit 26 shown in Figure 1, in addition to the resin stream inline 28, produces a solvent-extracted oil stream inline 56 and an asphaltene product stream inline 58. A portion of the resin may be withdrawn as a product stream inline 60. The product streams 40, 48, and 56 may be used individually, or may be combined as shown in Figure 1 to form a single synthetic crude product stream inline 62. - The present invention can be utilized for upgrading a variety of heavy viscous hydrocarbons including viscous crude oils, bitumens from tar sands, hydrocarbons derived from coal, lignite, peat or oil shale, re- sidium resulting from the vacuum or atmospheric distillation of lighter crude oils, heavy residues from solvent extraction processes, and the like. The basic process illustrated in Figure 1 is particularly suitable for use where the heavy viscous hydrocarbon feed has been previously processed leaving only those components boiling above 650°F (343°C) or higher in the feed.
- A modified process which would be more suitable for smaller units which process crude oils which have a significant amount of lighter fractions in the oil is shown in Figure 2. A heavy viscous hydrocarbon input or feedstock in
line 10 is fed throughconventional preheat exchangers feedstock heater 12 into a feedstock flash zone in a lower portion of adistillation column 14. Feedstock flash bottoms withdrawn inline 16 are passed through avisbreaker heater 18 and then into a visbreaker flash zone or intermediate zone of thedistillation column 14. Bottoms from the 'visbreaker flash zone are withdrawn in line 20 and supplied tosolvent extraction unit 26. Thesolvent extraction unit 26 produces a stream which contains a resin product at least a portion of which is combined with the material forming the feed for thevisbreaker furnace 18; for example, the resin inline 28 is fed into the bottom of thedistillation column 14 for combining with the feedstock bottoms which are subsequently withdrawn inline 16 to feed thevisbreaker heater 18. Gas and naphtha are withdrawn inline 30 as overhead from thedistillation column 14 and separated by theseparator 32 into a gas stream inline 34 and a naphtha stream inline 36. A portion of the naphtha stream inline 36 is fed back to the top of thecolumn 14 byline 38 as a reflux stream while the remaining portion forms a naphtha product inline 40. Gas oil is withdrawn in a side stream inline 42 from thedistillation column 14, with portions inlines stream 46 may be used as a quench 47 for thetransfer line 19 from the visbreaker heater. The remaining portion of the light gas oil forms a product stream inline 48. Where a. three-stage solvent extraction unit is employed as shown in Figure 2, thesolvent extraction unit 26, in addition to' the resin stream inline 28, produces a solvent-extracted oil stream inline 56 and an asphaltene product stream inline 58. A portion of the resin may be withdrawn as a product stream inline 60. The product streams 40, 48, and 56 may be used individually, or may be combined as shown in Figure 2 to form a single synthetic crude product stream inline 62. - The visbreaker heater may be of conventional coil only or coil plus soaking drum design or of any other available type. The term visbreaker heater as used herein includes all equipment associated with the visbreaker including the soaking drum where utilized but excluding the fractionator. The visbreaker heater heats the feedstock flash zone bottoms which includes the recycled resins to a temperature in the range from about 850 to 920°F (454 to 493°C). Generally a temperature near the lower end of the range will be utilized in the soaking :drum type visbreaker whereas a temperature near the higher end of the range will be employed in coil type visbreaking. The conversion within the
visbreaker heater 18 is limited to avoid coke formation. - Adding hydrogen to the visbreaking process improves yields. It also may be added to act as a chain reaction quench, to control feedstock residence time in the coil, to increase the amount flashed at the entrance of the distillation column, and to achieve some desulfurization. The preferred hydrogen addition point is usually near the furnace coil outlet where its chain-quenching effect is important in reducing coke formation. Alternatively, in some cases, it may be possible to absorb sufficient hydrogen in the preheated liquid feed before pumping to pressure to supply the amount of hydrogen required for chain-quenching. However, the hydrogen, if added, may be introduced at any point in the visbreaking process, depending on operating conditions and operator preference.
- In the
distillation column 14, the visbreaker effluent flashes up to a cut point as high as 840°F (449°C), depending on the temperature and hydrocarbon partial pressure in the visbreaker flash zone. The cut point and temperature in the visbreaker flash zone are selected as high as the coking tendency of the hydrocarbon will permit. - In order to minimize the size of the solvent extraction unit or to design to meet the capacity of an existing solvent extraction unit, a vacuum tower and vacuum heater may be added. To minimize the capital cost where the feedstock to the process is derived from bottoms, or other viscous heavy hydrocarbon where an initial topping is not particularly advantageous, the crude heater and crude flash zone in the
distillation column 14 may be eliminated and the flow scheme as shown in Figure 3 may be utilized. - The heavy viscous hydrocarbon feedstock in
line 10 is fed through preheat exchangers to an optional hydrogen contactor vessel/and then through avisbreaker heater 18 to the flash zone in thedistillation column 14. Bottoms from the flash zone are withdrawn in line 20 and :are at least partially vaporized in avacuum heater 21 and are then fed throughline 23 into avacuum column 22. Use of the vacuum heater will increase the cut point of the heavy gas oil and decrease the amount of the bottoms from the vacuum column throughline 24. This will decrease the required size of thesolvent extraction unit 26. Thesolvent extraction unit 26 produces a stream which contains resin product at least a portion of which is combined with the material forming the feed for thevisbreaker heater 18. Gas and naphtha are withdrawn inline 30 as overhead from thedistillation column 14 and separated by theseparator 32 into a gas stream inline 34 and a naphtha stream inline 36. A portion of the naphtha stream inline 36 is fed back to the top of thedistillation column 14 byline 38 as a reflux stream while the remaining portion forms a naphtha product inline 40.. Light gas oil is withdrawn in a side stream inline 42 from thedistillation column 14 with portions inlines stream 46 may be used as a quench 47 for thetransfer line 19 from the visbreaker heater. The remaining portion of the light gas oil forms a product stream inline 48. The liquid side stream from thevacuum column 22 is withdrawn as a heavy gas oil stream inline 50, a portion of which is recycled back as areflux stream 52 with the remainder forming a product stream inline 54. Where a three-stage solvent extraction unit is employed as shown in Figure 3, thesolvent extraction unit 26, in addition to the resin stream inline 28, produces a solvent-extracted oil stream inline 56 and an asphaltene product stream inline 58. A portion of the resin may be withdrawn as a prod- uct stream inline 60. The product streams 40, 48, 54 and 56 may be used individually, or may be combined to form one synthetic crude or several upgraded product streams.Conventional heat exchangers contactor vessel 13 may optionally be utilized for this or the hydrogen may be added directly in the pipeline. - A typical flow scheme for upgrading heavy viscous crudes such as Cold Lake, Athabasca, Lloydminister, Tia Juana, Pesado or Lagotreco, is shown in Figure 4. The hydrocarbon feedstock is heated to a temperature in the range from about 650 to 700°F (343 to 371°C).
Conventional heat exchangers crude heater 12 to bring the feedstock to the desired flash temperature for thedistillation column 14. - Crude flash bottoms withdrawn in
line 16 are passed through thevisbreaker heater 18 and then into a visbreaker flash zone or intermediate zone of thedistillation column 14. Bottoms from the visbreaker flash zone are withdrawn in line 20 and flashed as deeply as economically feasible within theadiabatic vacuum column 22. A 950°F (510°C) cut point can usually be obtained at a 40mm hydrocarbon partial pressure where the feed from the bottoms of the visbreaker flash zone contains only material with a boiling point above 650°F (343°C) and with its temperature at about 750°F (399°C). For minimum cost design, the cut point in the visbreaker flash ,zone of thedistillation column 14 is selected to be as high as practical to minimize the size of thevacuum column 22. This will result in a reduction in the quantity of vacuum bottoms being sent byline 24 to thesolvent extraction unit 26. The three-stagesolvent extraction unit 26 produces a resin product at least a portion of which is combined with the material forming the feed for thevisbreaker heater 18; for example, the resin inline 28 is fed into the bottom of thecolumn 14 for combining with the -crude bottoms which are subsequently withdrawn inline 16 to feed thevisbreaker heater 18. Gas and naphtha are withdrawn inline 30 as overhead from thedistillation column 14 and separated by theseparator 32 into a gas stream inline 34 and a naphtha stream inline 36. A portion of the naphtha stream inline 36 is fed back to the top of thecolumn 14 byline 38 as a reflux stream while the remaining portion forms a naphtha product inline 40. Light gas oil is withdrawn in a side stream inline 42 from thedistillation column 14 with portions inlines distillation column 14 as reflux streams. Part ofstream 46 may be used as a quench 47 for thetransfer line 19 from thevisbreaker heater 18. In lieu of or in addition to quench 47, vacuum bottoms may be recycled to the visbreaker flash zone throughline 49 or heavy gas oil may be used as a quench. The choice of quench schemes will depend on the feedstock characteristics and operator preference. The remaining portion of the light gas oil forms a product stream inline 48. The .liquid sidestream from thevacuum column 22 is withdrawn as a heavy gas oil stream inline 50, a portion of whirh is recycled back as areflux stream 52 with the remainder forming a product stream inline 54. The three-stagesolvent extraction unit 26 shown in Figure 4, in addition to the resin stream inline 28, produces a solvent-extracted oil stream inline 56 and an asphaltene product stream inline '58. A portion of the resin may be withdrawn as a product stream inline 60. The product streams 40, 48, 54 and 56 may be used individually, or may be combined to form a single synthetic crude product stream. - The improved process of the present invention renders possible the obtaining of residual and gas-free product yields greater than other nonhydroprocessing schemes and comparable to processes employing. high pressure hydroconversion. The prior art hydroconversion processes are much more costly both from an investment and operating standpoint, particularly due to catalyst cost, when compared with the present invention. Synthetic crude yield of prior art delayed coking processes are typically 5 to 7% by weight less on feed than the present inven- :tion, and the synthetic crude yield of prior art fluid coking processes are typically 2 to 4% by weight less.
- The increase in resin content of the feed to the
visbreaker heater 18 is principally responsible for the substantially increased yields of the present invention. The resins are found to act as peptizing agents and keep the very high molecular weight asphaltenes suspended. This maintenance in suspension of asphaltenes reduces the coking tendency in the visbreaker heater enabling a substantial increase in the conversion within the visbreaker heater without coking. Thus, a substantially higher conversion can be obtained in the visbreaker than without resin recycle. A high yield of synthetic crude of good quality is thus obtained utilizing relatively inexpensive thermal conversion rather than the more expensive hydroconversion processes. - Another advantage of the present invention is that the synthetic crude or products are relatively low in metal content and thus can be handled by conventional downstream processing such as catalytic cracking or hydrocracking. Metals content of some heavy crudes, such as Boscan and Cold Lake, are very high. High metals content results in catalyst deactivation due to pore plugging and screening of catalytically active sites if these high metal feeds are charged to a catalytic process. Thus prior art processes utilizing catalytic hydroconversion for primary conversion incur large catalyst costs due to the high metals content.
- When using normal pentane solvent extraction to deasphalt a crude, it is possible to obtain a yield of 57.6% oil plus resin; however, the oil plus resin contains 90 ppm of nickel plus vanadium. By reducing the yield of oil plus resin to 44% with normal pentane solvent, the metals content may be reduced to 51 ppm. The resin fraction contains approximately five times as much metal as the oil fraction. Thus recycling of the resin fraction results in substantially further reduction in metal content while substantially increasing maximum -yield. Thus by proper control of the solvent extraction procedure coupled with resin recycle through the visbreaker, substantial reduction in metal contents of synthetic crude is obtained while the yield is maintained.
- Still another advantage of the invention is the avoidance of cooling and reheating during process flow. The feeds to the
distillation column 14 are progressively heated, and, except where a vacuum heater is employed, the flows from the distillation column generally are progressively cooled resulting in substantially lower utility costs. Depending on the choice of solvent extraction scheme, some heating may also be required within the solvent extraction unit. Prior art hydroconversion processes generally require reheating and cooling producing substantially increased utility costs. Prior art delayed and fluid coking processes can be integrated to produce progressive heating and cooling similar to the present invention; however, the synthetic crude yield of such processes is substantially less than the present invention. - Further the present process offers advantages from the standpoint of hydrogen conservation. The recycle resins typically have a hydrogen content 15 to 20% higher than asphaltenes; the hydrogen content of a typical resin is 9.8 to 10.2% by weight, while asphaltenes have a hydrogen content of only 8.2 to 8.7% by weight. Thus a desirable greater hydrogen presence during thermal visbreaking is maintained. The bromine number, which measures the olefinic content, of a product from a fluid coking process is typically more than twice as high as that of a product produced in the present process, resulting in a much higher hydrogen consumption during subsequent hydroprocessing. A significant advantage of the process of this invention is that light hydrocarbon yields (Cl-C3) are approximately half of those listed in the literature for severe cyclic visbreaking to achieve a comparable tar yield, and only one fourth that of fluid coking. Since light hydrocarbons contain a high percentage of hydrogen, it is apparent that the liquid product from the process of this invention has a higher hydrogen content than that of competing processes; thus, downstream hydrotreating costs are significantly less. Thus conservation of hydrogen and rejection of only the minimum hydrogen content asphaltene results in minimum downstream refining costs.
- Several visbreaker runs were made in a visbreaker pilot plant using topped (650°F+) Cold Lake crude oil and mixtures of this same topped crude with a composite of resin fractions obtained from solvent extraction of the products from previous visbreaker runs. The pilot plant consisted of a feed charge drum, a feed pump, metering equipment and five electric furnaces, each 4 ft. long, through which passed 0.43" ID x 22'6" ft. long stainless steel tubing used as the visbreaking coil, a cooler for quenching the furnace outlet, a back pressure regulating valve, and a receiver in which all products, gas and liquid, were accumulated. Conditions for 'these runs, together with the characteristics of the feed and visbreaking yields are presented as Table I.
- Run -1 represents a visbreaker run with no resin recycle at typical conditions for a commercial visbreaker. Run 2 is a visbreaker run with resin recycle equal to 20% of the total visbreaker feed at about the same severity as
Run 1. Run 3 is a visbreaker run at higher severity thanRuns 1 and 2 and with resin recycle equal to 20% of the total visbreaker feed; theory being that resins stabilize the asphaltenes in the oil and reduce coke formation in the visbreaker furnace. - Using the yield data of Run 2 and subtracting 80% of the yield data of
Run 1, yield data for the recycled resin can be derived. This calculation is shown'in Table III. It should be noted that at approximately the same severity asRun 1, for Run 2 the resin went approximately half to-asphalt and half to solvent extracted oil. The apparent negative yield from recycle resin of the 650-950°F fraction in Run 2 is probably accounted for by experimental error. - The most important aspect of visbreaking is the conversion of the 950°F+ material to lower boiling products and products with lower contents of Conradson carbon and metals. Table IV presents a summary of the results of
Runs 1, 2, and 3 with respect to the disposition of the 650°F+ fractions. Several important observations and conclusions can be drawn from the information in Table IV together with the information in Table II. - (1) The resin fraction has the highest conversion rate of the various fractions, approximtely ten times greater than the average of the high molecular weight oils. For
Runs 1 and 2, at about the same severity, about 65% of the resin is converted and for Run 3 at the higher severity, 71% is converted. - (2) At the higher severity of Run 3 compared to Run 2, and .with the same feedstock including recycle resin, the following observations can be made:
- a) That the asphaltene yield is lower (1.39 parts/part feed compared to 1.51 parts/part feed) at the higher severity of Run 3. This illustrates the synergism resulting from resin recycle because a higher yield of asphaltene would be expected at higher severity without resin recycle.
- b) That the yield of 950°F+ solvent extracted oil is 0.68 parts/part of feed for Run 3 compared to 0.97 parts/part of feed for Run 2. This result indicates that the 950°F+ oil fraction is converted to more useful lower boiling products at the higher severity without resulting in a higher asphaltene yield.
- c) That the 650-950°F fraction shows an increase for Run 3, 1.13 parts/part of feed, compared to 0.85 parts/part of feed for Run 2. This confirms that the 950°F+ fractions of asphaltenes, resins, and oil are converted to a greater percentage of useful lower boiling fractions at the higher severity.
- (3) The Conradson carbon content as well as the metals content of the 950°F+ solvent extracted oil for the test runs with resin recycle range from 10.9% to 11.3% and 38 ppm to 56 ppm, respectively.
- These values are high for a good feedstock to downstream catalytic processes such as catalytic cracking or.hydrocracking. The quality of the solvent extracted oil could be greatly improved, e.g., to 3 to 4% Conradson carbon and 10 to 20 ppm metals, by using a lighter solvent such as isobutane or propane rather than n-pentane. The use of the lighter solvent would reduce the per pass oil yield; however, taking into consideration that resin is recycled to extinction, the overall yield of the higher quality 950°F+ oil and lower boiling products would be the same or higher as compared to the n-pentane solvent cases. This additional resin recycle can be accomplished with minimal effect on the capital and operating costs of the unit.
- A further extension of this concept would be to produce a combined resin and oil fraction from the 950°F+, or 1050°F+ by revising vacuum column operating conditions, material and recycle that fraction to extinction; in this case there would be zero yield of the 950°F+, or 1050°F+, oil and all products, other than the asphaltene fraction, would be distillate products very low in Conradson carbon and metals content.
- By utilizing pilot plant data, one can calculate the product yields of a process performed in accordance with the invention. 20,000 barrels per day of 10.8° API Cold Lake crude are upgraded in the process as illustrated in Figure 4. The recycle bottoms in
line 16 have a boiling point greater than 650°F (343°C). The bottoms from the visbreaker flash zone in line 20 have a boiling pont above 700°F (371°C). The naphtha inline 36 has a boiling point less than 400°F (204°C) while the boiling range for the light gas oil inline 48 is in the range from 400 to 700°F (204 to 371°C). The heavy gas oil inline 54 has a boiling point in the range from 700 to 950°F (371 to 510°C). The synthetic crude product inline 62 forms a stream of about 17,360 barrels per day or approximately 86.8% volume of the feedstock at 21.8° API and 20 centistokes viscosity at 100°F. In the total output, the gas inline 34 forms about 1.3% by weight, the naptha inline 40 forms about 13.2% by volume, the light gas oil inline 48 is about 30.8% by volume, the heavy gas oil inline 54 is about 22.3% by volume, the solvent-extracted oil inline 56 is about 20.5% by volume, and the asphaltene inline 58 is about 14.9% by volume of the total input. About 4.9% of the total volume is recycled inline 28 as resin. - Since many modifications, variations and changes in detail may be made to the process described above, it is intended that all matter described in the foregoing description and shown in the accompanying drawings be interpreted as illustrative and not in a limiting sense.
Claims (8)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US477948 | 1983-03-23 | ||
US06/477,948 US4454023A (en) | 1983-03-23 | 1983-03-23 | Process for upgrading a heavy viscous hydrocarbon |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0121376A2 true EP0121376A2 (en) | 1984-10-10 |
EP0121376A3 EP0121376A3 (en) | 1986-01-08 |
EP0121376B1 EP0121376B1 (en) | 1989-01-25 |
Family
ID=23897966
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84301888A Expired EP0121376B1 (en) | 1983-03-23 | 1984-03-20 | Process for upgrading a heavy viscous hydrocarbon |
Country Status (6)
Country | Link |
---|---|
US (1) | US4454023A (en) |
EP (1) | EP0121376B1 (en) |
JP (1) | JPS59179695A (en) |
CA (1) | CA1210358A (en) |
DE (1) | DE3476419D1 (en) |
MX (1) | MX163737B (en) |
Cited By (2)
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EP0434799A1 (en) * | 1989-07-18 | 1991-07-03 | Amoco Corp | Resid hydrotreating with solvent-extracted and desasphalted resins. |
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FR2939804A1 (en) * | 2008-12-11 | 2010-06-18 | Total Raffinage Marketing | Converting petroleum charges (having e.g. heavy crude), comprises deasphalting oil with heavy solvent and light solvent comprising saturated hydrocarbon, converting deasphalted oil by catalytic cracking and converting pitch by visbreaking |
Also Published As
Publication number | Publication date |
---|---|
DE3476419D1 (en) | 1989-03-02 |
CA1210358A (en) | 1986-08-26 |
JPS59179695A (en) | 1984-10-12 |
JPH0552350B2 (en) | 1993-08-05 |
EP0121376A3 (en) | 1986-01-08 |
EP0121376B1 (en) | 1989-01-25 |
US4454023A (en) | 1984-06-12 |
MX163737B (en) | 1992-06-17 |
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